CN101423469A - Oxidation process for aromatic compound - Google Patents
Oxidation process for aromatic compound Download PDFInfo
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- CN101423469A CN101423469A CNA2007101966353A CN200710196635A CN101423469A CN 101423469 A CN101423469 A CN 101423469A CN A2007101966353 A CNA2007101966353 A CN A2007101966353A CN 200710196635 A CN200710196635 A CN 200710196635A CN 101423469 A CN101423469 A CN 101423469A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
Abstract
The invention can use tert-butyl hydroperoxide and microwave radiation for oxidizing the methylene-substituted aromatic compound. Specially, xylol mainly generates benzene dicarboxylic acid, and toluene generates benzoic acid. The methylene-substituted aromatic compound generates ketone and does not generate acid, wherein the methylene is not methyl part. For example, fluorene generates fluorenone. The method prevents the requirement of existence of metal in catalyst or oxidant. Furthermore the water can be used and the organic solvent is not required. Therefore the method can accord with the ideal of green chemistry.
Description
Technical field
The present invention relates to a kind of method for oxidation.More specifically, it relates to the aromatic substance that will replace and is oxidized to ketone or carboxylic acid.
Background technology
Oxidation is that the feedstock conversion with the petroleum chemistry base becomes the more core technology of the general chemical of high oxidation state (commodity chemicals).Yet oxidizing reaction has proposed some great challenges to environment.Many industrial method for oxidation relate to heavy metal or corrosive reagents, and the energy expenditure height.
The selectivity benzylic oxidation that the aromatic substance that alkyl replaces becomes ketone or carboxylic acid is important laboratory and commercial organic transformation basically
1,2,3Oxidation products is the basic intermediate that is used to prepare high value fine chemicals, agrochemicals, pharmaceuticals and high tonnage commodity
4,5Such benzylic oxidation can be finished by various oxygenants such as permanganate and chromic salt based on transition metal.If molecular oxygen, hydrogen peroxide or hydroperoxide as oxygenant, are needed the catalyzer of homogeneous or heterogeneous metal matrix (metal-based) so
2,6
For example, terephthalic acid is that the oxidation by right-dimethylbenzene produces under aggressive conditions.Terephthalic acid is one of preceding 50 kinds of industrial chemicals, and annual global demand amounts to 4,000 ten thousand tons, and the annual about 5-10% of rate of increase
6It is the principal monomer of polyethylene terephthalate (PET).PET is a general raw material of making soda bottle and other packaging resin.Also making of weaving by terephthalic acid with synthetic fiber such as polyester (terylene).
In the commercial run of preparation terephthalic acid, under 200 ℃ and 20atm pressure in acetate with atmospheric oxidation right-dimethylbenzene.Catalyst system is made by the salt of heavy metal bromide and cobalt and manganese.Because reaction mixture is a high corrosion, so described reaction must be carried out in the reactor of titanium lining.On the other hand, by fluidized-bed V
2O
5The catalyzer of base carries out the gaseous oxidation of ortho-xylene to phthalic acid.Phthalic acid is the main precursor of many softening agent.In all these known method for oxidation of methyl aromatic substance, need the oxygenant or the catalyzer of metal matrix.If air as oxygenant, is usually directed to high reaction temperature and pressure so.
In recent years, the method that is used to produce the Environmental awareness of carbon and aromatic feedstock for exploitation has been carried out a large amount of effort
7,8,9For example, and since their toxicity, negative environmental influence, and need remove metal remained from reaction product, so should avoid using heavy metal.If can not abandon fully, also should reduce the use of organic solvent, to reduce the VOC discharging.It is said that this so-called Green Chemistry will be the future of sustainable chemical industry.
Summary of the invention
The purpose of this invention is to provide a kind of method for oxidation, described method is more environmentally acceptable, and does not require that particularly the use metal is such as heavy metal.In relevant purpose, if the ideal words can be avoided the needs to organic solvent.
The inventor is provided for the oxidation step of the aromatic substance of oxidation methylene radical replacement, and described oxidation step use tert-butyl hydroperoxide (TBHP) are as oxygenant and use microwave radiation as energy source, to produce ketone or carboxylic acid.
Particularly, dimethylbenzene usually with other sour admixture in produce phthalic acid, and toluene produces phenylformic acid.Wherein methylene radical is not the aromatic substance generation ketone of other methylene radical replacement of methyl moiety, rather than acid.For example, fluorenes produces Fluorenone.Described method is avoided need be such as existing metal in catalyzer or oxygenant, and water rather than organic solvent are carried out.
Description of drawings
Fig. 1 provides and uses before TBHP and the microwave irradiation oxidation and the photo of right-dimethylbenzene afterwards.
Embodiment
Present method typically adopts excessive TBHP.For the oxidation that is not the aromatics methylene compound of aromatics methyl compound, TBHP: the mol ratio of aromatic substance is suitably 2:1 at least, such as 5:1 at least; Such as about 10:1.For the oxidation of aromatics methyl compound, higher ratio is an ideal, preferred 15:1 at least, or more preferably 25:1 at least; Such as about 20:1 or 30:1.
Temperature of reaction usually in 100 ℃ of-220 ℃ of scopes, such as 140 ℃-190 ℃, preferably 145 ℃-195 ℃.Such temperature obtains by the radiation with suitable power and frequency.
Duration of the reaction is usually from 20 minutes to 5 hours, such as 40 minutes to 4 hours, and preferred about 1 hour.
In one aspect, the invention provides the oxidation of following formula I compound:
Wherein R is the group that is selected from hydrogen, alkyl and aryl; With
R
1Be the one or more substituting groups that are selected from hydrogen, alkyl, alkoxyl group, halogen, hydroxyl, amino, cycloalkyl, aryl or alkylhalide group;
Perhaps R and adjacent R
1Formation can self be substituted or the condensed ring key.
Alkyl preferably has 1-6 carbon atom, particularly 1 or 2 carbon atom.Aryl and aromatic substance be hydrocarbon preferably, and phenyl normally.The moieties of alkoxyl group preferably such as qualification.Halogen comprises chlorine and bromine.Amino can be simple amino (simple amino), perhaps uncle or uncle's amino.Cycloalkyl preferably has 3-8 carbon atom.
1 or 2 R is arranged usually
1Group, preferred 1 R
1Group.
Preferred compound comprises that R wherein is those of hydrogen, and is such as toluene and three kinds of dimethylbenzene, particularly right-dimethylbenzene.
Other preferred compound comprises ditan and ethylbenzene.
As R and R
1When forming ring key, it can be a polymethylene, such as-(CH
2) n-, for example, wherein n is 2 or 3.Described key can self and aromatic nucleus condense.This examples for compounds comprises fluorenes and tetraline.
The result of oxidation depends on whether R is hydrogen.
Therefore, toluene produces phenylformic acid.Dimethylbenzene typically produces phthalic acid, tolyl acid and benzoic mixture.The amount of phthalic acid is greater than the method for other acid product summation in the preferred wherein mixture of the inventor.
Preferably, described method does not have metal and organic solvent.Particularly, described method can be carried out not existing under metal catalyst such as the heavy metal catalyst.In addition, although the omission of organic solvent is not enforceable, described method can be carried out without organic solvent.Typically, though do not comprise organic solvent in aspect more preferred, particularly polar solvent such as uncle-butanols, oil of mirbane or acetonitrile, the inventor adopts water-based TBHP.
More specifically, TBHP (tert-butyl hydroperoxide) such as 70% water-based TBHP with for example at the microwave irradiation of 2450Mhz, can produce the green oxidation flow process of the aromatic substance that is used for the alkyl replacement.Methyl aromatic substance (toluene or dimethylbenzene) can be direct oxidation into industrial important carboxylic acid and dicarboxylic acid.(0.1-5% is such as 1-4%, preferably such as the about 2%) ionic liquid of adding trace and/or cooling simultaneously can improve oxidation efficiency.Aromatic substance and relevant compound for other alkyl replaces obtain ketone with good yield.Reaction medium is water preferably.Do not need the reagent of organic solvent, metal matrix or the catalyzer of metal matrix.
TBHP is the cheap oxygenant of industrial widespread use
10,11Than spissated hydrogen peroxide, TBHP is for the thermolysis quite stable.In fact, 70% water-based TBHP constitutes large organic chemicals (bulk organic chemicals), and has been identified in many countries and is used for truck shipment (truck shipment).
The organic synthesis of microwave-assisted is the research field of growing up fast
12-16Think that at first present technique is to be used to be generally the method that the order of magnitude reduces the reaction times, and be the method for cleaning activity that is used to have the product yield of increase.In addition, it is also for providing chance by the infeasible new reaction of conventional heating means in addition
15Carry out a kind of analogy, microwave reaction will become " the Bunsen burner of 21 century "
12,17
Embodiments of the invention
Method
Use CEM Discover Unit (CEM Corporation, NC, USA), in 10mL Glass Containers with the sheet rubber sealing, with alr mode in the experiment that has or not have to use under the while refrigerative situation 0.2-0.5 mmole substrate.Target setting temperature and maximum microwave power (for not or have the reaction of ionic liquid be respectively 250 and 80W).In several minutes, reach target temperature.During reaction, microwave power and pressure (60-240psi) change.
For the oxidation of toluene, develop easily the NMR method and monitor reaction.Take out the sample of reaction mixture and use CDCl
3Dilution.Use D
2After O handles, record
1H NMR (270MHz) spectrum.Percentage conversion can from the phenylformic acid aromatics proton signal of abundant parsing (for-, right-and neighbour-proton be respectively 7.41-7.47,7.54-7.57 and 8.05-8.08ppm) and the integral and calculating of the methyl signals (2.35ppm) of toluene.
One preferred aspect in, oxidation of the present invention is as shown in scheme 1:
Scheme 1
The benzylic oxidation of the aromatic substance that alkyl replaces
Embodiment 1
The benzylic aromatic substance that inventor's original research methylene radical replaces is oxidized to ketone (scheme 1, R ≠ H).When with the mixture of fluorenes and 10 normal 70% water-based TBHP in sealed vessel during with microwave irradiation 10 minutes (250W, 170 ℃), the almost Fluorenone (table 1) of quantitative yield of emanating.Experiment in contrast is when the inventor only in the time of 8 hours, has only the Fluorenone of trace to detect by TLC identical reaction mixture refluxed by conventional oil bath heating.Oxidation with another kind of substrate ditan of dual activatory benzylic position also provides benzophenone with high yield.For single activatory methylene unit, ethylbenzene also carries out to the oxidation of α-Tetralone an intermediate of Sertraline smoothly to methyl phenyl ketone and tetraline under this green flow process.The result is summarised in the table 1.
Table 1 aromatic substance that alkyl replaces under microwave irradiation is to the TBHP oxidation of ketone
Running substrate condition product yield
1
170℃，10min
98％
2
180℃，30min
85％
3
180℃，30min
77％
4
170℃，30min
53％
Embodiment 2
Along with the initial success in the oxidation of methylene radical benzylic unit, the inventor is devoted to the oxidation of more challenging methyl substituted aromatic substance then.
At first toluene is used as model research to benzoic oxidation.Use 6 normal 70% water-based TBHP (excessive 2 times), 160 ℃ under microwave irradiation 1hr toluene change into phenylformic acid (running 1, table 2) with 9.1%.Prove that fully the solvent with high-k will improve the microwave heating effect.When oxidizing reaction uncle-butanols, oil of mirbane or acetonitrile as cosolvent in (running 2,3,4) when carrying out, percentage conversion is increased to 20-27%.The inventor has also studied other TBHP prescription such as the TBHP in octane-iso and the toluene
18,19Application.Oxidation still can take place, but the result is not as making the result of use TBHP.
Experiment in contrast, the inventor carried out described oxidizing reaction in 7 hours by conventional reflux (130 ℃).There is not phenylformic acid from reaction mixture, to detect.In addition, microwave reaction must carry out in sealed vessel.When in open containers when 104-114 ℃ of reflux temperature uses microwave heating to carry out described reaction, do not have phenylformic acid to detect.
Table 2 toluene under microwave irradiation arrives benzoic TBHP oxidation
| Running | G | Toluene/TBHP | Condition | Transformation efficiency |
| 1 | H | 1:6 | Pure, 160 ℃ | 9.1％ |
| 2 | H | 1:6 | t-BuOH，160℃ | 20％ |
| 3 | H | 1:6 | C 6H 5NO 2，160℃ | 26％ |
| 4 | H | 1:6 | CH 3CN，160℃ | 27％ |
| 5 | H | 1:6 | 2% ionic liquid, 160 ℃ | 29％ |
| 6 | H | 1:20 | 2% ionic liquid, 150 ℃ | 41％ |
| 7 | H | 1:20 | 2% ionic liquid, 150 ℃ of coolings simultaneously | 69％ |
| 8 | H | 1:20 (1mmol) | 2% ionic liquid, 150 ℃, 2hr cools off simultaneously | 94％ |
| 9 | o-Cl | 1:20 | 2% ionic liquid, 150 ℃ of coolings simultaneously | 46％ |
| 10 | m-Cl | 1:20 | 2% ionic liquid, 150 ℃ of coolings simultaneously | 50％ |
| 11 | p-Cl | 1:20 | 2% ionic liquid, 150 ℃ of coolings simultaneously | 57％ |
| 12 | p-Br | 1:20 | 2% ionic liquid, 150 ℃ of coolings simultaneously | 51％ |
| 13 | o-NO 2 | 1:20 | 2% ionic liquid, 150 ℃ of coolings simultaneously | 39％ |
| 14 | p-OEt | 1:20 | 150 ℃ of coolings simultaneously | 80％ |
Recently, reported that a spot of ionic liquid of adding can greatly increase the heating efficiency of microwave reaction
20-22In order to improve the yield of toluene oxidation, carry out the TBHP oxidation with Tetrafluoroboric acid 1-butyl-3-methylimidazole salt (1-butyl-3-methylimidazolium tetrafluoroborate) of 2%.With 9.1% comparing of not having ionic liquid, transformation efficiency is increased to 29% (running 5 is with respect to 1).
In all crude product mixture
1In the H NMR spectrum, the inventor 2.17 and 3.46ppm continue to observe the unimodal of two mysteries.The methyl of these NMR peaks corresponding acetone of difference and methyl alcohol.The inventor infers that TBHP resolves into acetone and methyl alcohol under described reaction conditions.In order to confirm this supposition, under microwave irradiation, the 70%TBHP sample is heated half an hour at 160 ℃.Reaction mixture
1H NMR spectrum has confirmed the inventor's supposition.
The mechanism of two kinds of propositions of this TBHP decomposition has been described in scheme 2.Similar to the thermolysis of cumene hydroperoxide (cumene hydroperoxide) in acidic medium, the ionic approach comprises the fracture of weak peroxide bond, and methyl is moved on the electron deficiency peroxy oxygen then.Alternatively, free radical mechanism can be explained this observation.
The decomposition of scheme 2TBHP under microwave irradiation
Consider this decomposition, the inventor is increased to 20 equivalents with the amount of TBHP.Transformation efficiency is increased to 41% (running 6).
When using ionic liquid, heat very fully, so that reaction mixture can be easily in seconds overheated.Therefore, microwave power can not be provided with too high (the 80W contrast does not have the 250W of the experiment of ionic liquid).In addition, after reaching preset temp, microwave power drops to quite low level (about 30W).Keep reaction for the microwave energy that keeps reasonable level, the inventor has attempted recently at document
23The idea of middle report.During microwave irradiation, the pressurized air or the nitrogen gas stream of room temperature are passed through reaction vessel.
Add that when using ionic liquid when cooling off simultaneously, (1hr) microwave power can remain on 70-40W in reaction process.Percentage conversion is brought up to 69% (running 7).In order to promote toluene oxidation to finish, microwave reaction (1mmol toluene and 20mmol 70%TBHP and 67mg Tetrafluoroboric acid 1-butyl-3-methylimidazole salt) (running 8) carried out 2 hours, cooling simultaneously.Obtain 94% transformation efficiency.Behind simple post-treatment and the recrystallization, with good yield segregation phenylformic acid.
Also carried out the oxidation of the toluene of replacement, and the result lists (running 9-13) in table 2.Obviously, the electrophilic substituting group oxidising process that slowed down.Further be reduced to-20 ℃ (from high-pressure liquid nitrogen jars) by temperature, just improved the efficient of TBHP direct oxidation slightly cooling gas.
The free radical mechanism of the proposition of this microwave-assisted direct oxidation has been described in the scheme 3.When microwave irradiation, the inventor supposes that TBHP fragments into uncle-butoxide and hydroxyl radical free radical.Provide benzyl radicals from the methylbenzene extraction hydroperoxyl radical, described benzyl radicals combines with hydroxyl radical free radical and produces phenylcarbinol.Further oxidation can produce phenyl aldehyde (or its hydrate), is phenylformic acid then.In fact, if the inventor is limited in 4 equivalents with the amount of TBHP, so at reaction mixture
1Detect the phenyl aldehyde of small quantity in the H NMR spectrum.
The mechanism of scheme 3 microwaves-auxiliary TBHP oxidation
As shown in scheme 4, also carried out the direct oxidation of 70% water-based TBHP of 3 kinds of xylene isomers under the cooling at the same time and 30 equivalents (5 times excessive).
The TBHP oxidation of dimethylbenzene under scheme 4 microwave irradiations
P-CH
3Terephthalic acid 4a
M-CH
3M-phthalic acid 4b
O-CH
3Phthalic acid 4c
The result is summarised in the table 4.In these situations, the application of ionic liquid is not crucial.The oxidation of dimethylbenzene may be a process progressively.In crude product mixture, also obtained the tolyl acid (tolyl acid) of different amounts.This conforms to the following fact: the easiness of the toluene oxidation of replacement and the electron density of aromatic nucleus be (the clauses and subclauses 9-13 of table 2) quite.In case a methyl of dimethylbenzene is oxidized, the oxidation that remains methyl is so deactivated by the electrophilic effect of carboxyl
24Make the inventor surprised be also to detect the phenylformic acid of 5-10%.
Except the xylene isomer oxidation produced product mixtures, the segregation of two kinds of products also was direct.Right-and-situation of dimethylbenzene in, the benzene dicarboxylic acid of oxidation (terephthalic acid 4a and m-phthalic acid 4b) is precipitated out (referring to side information (being reference)) from reaction mixture.Behind filtration and the recrystallization, can obtain the terephthalic acid and the m-phthalic acid of purifying with medium yield.
Table 4
In a word, this is the direct microwave-assisted oxidation of reported first without any the Alkylaromatics of metal catalyst.The aromatic substance that alkyl replaces also can become eco-friendly Green Chemistry process to the oxidation of ketone, list and dicarboxylic acid.This carries out not existing under the heavy metal, and randomly also carries out not existing under the organic solvent.The solvent that needs only is a water of following TBHP
16,25-27Can use a spot of ionic liquid in the oxidation of toluene, it also is considered " green " reagent
28-30At last, compare with the routine heating, the microwave of focusing also is highly effective " green " energy
31,32
Xylene isomer is oxidized to corresponding phthalic acid and has opened up green alternatives for synthetic these important economically fine chemicals.For in viable commercial, the inventor recognizes may need to improve yield.Use continuous flow reactor
33,34Can be feasible.In the continuous flow system, the diacid that can elimination be precipitated out, and with the solution recycle back in microwave reaction.Be applied to other organic compound well afoot along the work of this direction and with this green oxidation flow process.
Reference
1.Hudlicky，M.Oxidation in Organic Chemistry(American ChemicalSociety，Washington，DC，1990).
2.Hughes，M.D.，Xu，Y-J.，Jenkins，P.，McMorn，P.，Landon，P.，Enache，D.I.，Carley，A.F.，Attard，G.A.，Hutchings，G.J.，King，F.，Stitt，E.H.，Johnston，P.，Griffin，K.& Kiely，C.J.Tunable gold catalyst for selectivehydrocarbon oxidation under mild conditions.Nature 437，1132(2005).
3.Bonvin，Y.，Callens，E.，Larrosa，I.，Henderson，D.A.，Oldham，J.，Burton，& A.J.，Barrett，A.G..M.Bismuth-catalyzed benzylic oxidation withtert-butyl hydroperoxide.Organic Letters 7，4549(2005).
4.Sheldon，R.A.& Bekkum，H.Fine Chemicals Through HeterogeneousCatalysis，Chapter 9(Wiley-VCH，Weinheim，2001).
5.Wittcoff，H.A.，Reuben，B.G.& Plotkin，J.S.Industrial OrganicChemicals(Wiley，New Jersey，ed.，2004).
6.Weissermel，K.& Arpe，H.-J.Industrial Organic Chemistry(Wiley-VCH，Weinheim，ed.4，2003).
7.Poliakoff，M.，Fitzpatrick，J.M.，Farren，T.R.& Anastas，P.T.Greenchemistry：science and politics of change.Science 297，807(2002).
8.An example for green production of adipic acid：Sato，K.，Aoki，M.&Noyori，R.A‘green’route to adipic acid：direct oxidation of cyclohexeneswith 30 percent hydrogen peroxide.Science 281，1646(1998).
9.Noyori，R.，Aoki，M.& Sato，K.Green oxidation with aqueous hydrogenperoxide.Chem.Commun.1977-1986(2003).
10.Sharpless，K.B.& Verhoeven，T.R.Metal-catalyzed，highly selectiveoxygenations of olefins and acetylenes with tert-butyl hydroperoxide.Practical considerations and mechanisms.Aldrichim.Acta.12，63(1979).
11.Sheldon，R.A.in The Chemistry of Peroxides(ed Patai，S.)(Wiley，NewYork，1983)
12.For a recent review see：Kappe，C.O.Controlled microwave heating inmodem organic synthesis.Angew.Chem.，Int.Ed.43，6250(2004).
13.
，P.& Tierney，J.P.，Eds.Microwave-Assisted Organic Synthesis(Blackwell，Oxford，2005).
14.Loupy，A.，Ed.Microwave in Organic Synthesis(Wiley-VCH：Weinheim，2002).
15.Miyazawa，A.，Tanaka，K.，Sakakura，T.，Tashiro，M.，Tashiro，H.，Prakash，G.K.S.& Olah，G.A.Microwave-assisted direct transformation of aminesto ketones using water as an oxygen source.Chem.Commun.2104(2005).
16.Leadbeater，N.E.Fast，easy，clean chemistry by using water as a solventand microwave heating：the Suzuki coupling as an illustration.Chem.Commun.2881(2005).
17.The term was first coined by Bose，A.K.：Bose，A.K.，Banik，B.K.，Lavolinskaia，N.，Jayaraman，M.& Manhas，M.S.MORE chemistry in amicrowave.Chemtech，27，18(1997).
18.Katsuki，T.& Martin，V.in Organic Reactions(ed Paquette，L.A.)Vol 48，pp1-299(1996).
19.Hanson，R.M.& Sharpless，K.B.Procedure for the catalytic asymmetricepoxidation of allylic alcohols in the presence of molecular sieves J.Org.Chem.51，1922(1986).
20.Ley，S.V.，Leach，A.G.& Storer，R.I.A polymer-supported thionatingreagent.J.Chem.Soc.Perkin Trans.1358(2001).
21.Leadbeater，N.E.& Torenius，H.M.A study of the Ionic liquid mediatedmicrowave heating of organic solvents.J.Org.Chem.67，3145(2002).
22.Leadbeater，N.E.，Torenius，H.M.& Tye，H.Ionic liquids as reagents andsolvents in conjunction with microwave heating：rapid synthesis of alkylhalides from alcohols and nitriles from aryl halides.Tetrahedron 59，2253(2003).
23.Arvela, R.K.﹠amp; Leadbeater, N.E.Suzuki coupling of aryl chlorides withphenylboronic acid in water, using microwave heating with simultaneouscooling.Organic Letters 7,2101 (2005) and reference wherein.
24.Parshall，G.W.& Ittel，S.D.Homogeneous Catalysis(Wiley，New York，ed.2，1992).
25.Li，C.-J.& Chen，L.Organic chemistry in water.Chem.Soc.Rev.35，68-82(2006).
26.
U.M.& Andersson，F.Hydrophobically directed organicsynthesis.Angew.Chem.Int.Ed.45，548-551(2006).
27.Narayan，S.，Muldoon，S.，Finn，M.G.，Fokin，V.V.，Kolb，H.C.&Sharpless，K.B.“On water”：unique reactivity of organic compounds inaqueous suspension.Angew.Chem.，Int.Ed.44，3275(2005)
28.Rogers，R.D.& Seddon，K.R.Eds.Ionic Liquids as Green Solvents(ACSSymposium Series 856，American Chemical Society，Washington DC，2003)
29.Rogers，R.D.& Seddon，K.R.Eds.Ionic Liquids Industrial Applicationsto Green Chemistry(ACS Symposium Series 818，American ChemicalSociety，2002).
30.Wasserscheid，P.& Welton，T.Eds.Ionic Liquids in Synthesis(Wiley-VCH，Weinheim，2003)
31.Nüechter，M.，Ondruschka，B.，Bonrath，W.& Gum，A.Microwaveassisted synthesis-a critical technology overview.Green Chem.6，128(2004).
32.Chark，J.& Macquarie，D.Eds Handbook of Green Chemistry andtechnology(Blackwell，Oxford，2002).
33.Comer，E.& Organ，M.G.A Microreactor for microwave-assistedcapillary(continuous flow)organic synthesis.J.Am.Chem.Soc.127，8160(2005).
34.Bagley，M.C.，Jenkins，R.L.，Lubinu，M.C.，Mason，C.& Wood，R.Asimple continuous flow microwave reactor.J.Org.Chem.70，7003(2005).
Claims (10)
1. the method for the aromatic substance that replaces of oxidation methyl or methylene radical, described method comprises the aromatic substance of using tert-butyl hydroperoxide and the described methyl of microwave radiation oxidation or methylene radical to replace.
2. the process of claim 1 wherein that described oxidation carries out in aqueous systems.
3. the method for claim 2, wherein said oxidation are carried out not existing under the metal-based catalyst.
4. the method for claim 2, wherein said oxidation are carried out not existing under the metal matrix oxygenant.
5. an oxidation aromatics methyl compound produces the method for aromatic carboxylic acid, and described method comprises with microwave radiation shines described aromatics methyl compound, simultaneously described aromatics methyl compound is contacted with the tert-butyl hydroperoxide.
6. the method for claim 5, wherein said aromatics methyl compound is that toluene and described acid are phenylformic acid.
7. the method for claim 5, wherein said aromatics methyl compound is that ortho-xylene and described acid are phthalic acids.
8. the method for claim 5, wherein said aromatics methyl compound be between-dimethylbenzene and described acid are m-phthalic acids.
9. the method for claim 5, wherein said aromatics methyl compound is that right-dimethylbenzene and described acid are terephthalic acids.
10. an oxidation aromatics methylene compound produces the method for aromatic ketone, described aromatics methylene compound is not the aromatics methyl compound, described method comprises with microwave radiation shines described aromatics methylene compound, simultaneously described aromatics methylene compound is contacted with the tert-butyl hydroperoxide.
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| CN102115353A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院大连化学物理研究所 | Method for selective oxidization of aromatic hydrocarbons |
| CN105152830A (en) * | 2015-09-15 | 2015-12-16 | 河南师范大学 | Method for synthesizing ketone compound |
| CN108467342A (en) * | 2018-04-08 | 2018-08-31 | 中南大学 | A kind of method of ultrasonic wave assisted oxidation benzyl alcohol class compound synthesis benzoic acid derivative |
| CN108610251A (en) * | 2018-05-08 | 2018-10-02 | 宁波大学 | A kind of efficient aromatic hydrocarbons catalysed oxidation processes |
| CN111777556A (en) * | 2020-07-15 | 2020-10-16 | 遂成药业股份有限公司 | Method for preparing acridine 9-carboxylic acid by oxidation method |
| CN112321414A (en) * | 2020-10-13 | 2021-02-05 | 华南理工大学 | Method for preparing benzene carboxylic acid by methyl-substituted benzene liquid-phase oxidation |
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| US8754254B2 (en) | 2010-06-30 | 2014-06-17 | Uop Llc | Process for purifying terephthalic acid |
| US8884055B2 (en) | 2010-06-30 | 2014-11-11 | Uop Llc | Process for producing terephthalic acid |
| US8933265B2 (en) | 2010-06-30 | 2015-01-13 | Uop Llc | Process for oxidizing alkyl aromatic compounds |
| US8884054B2 (en) | 2010-06-30 | 2014-11-11 | Uop Llc | Process for oxidizing alkyl aromatic compounds |
| US8933266B2 (en) | 2010-06-30 | 2015-01-13 | Uop Llc | Process for producing terephthalic acid |
| US8835678B2 (en) | 2010-06-30 | 2014-09-16 | Uop Llc | Solid terephthalic acid composition |
| US9045407B2 (en) | 2010-06-30 | 2015-06-02 | Uop Llc | Mixtures used in oxidizing alkyl aromatic compounds |
| CN102093224A (en) * | 2011-01-26 | 2011-06-15 | 北京工业大学 | Method for synthesizing nitrobenzoic acid by using microwaves |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9113476D0 (en) * | 1991-06-21 | 1991-08-07 | Interox Chemicals Ltd | Oxidation of alkylaromatics |
| GB9213420D0 (en) * | 1992-06-24 | 1992-08-05 | Solvay Interox Ltd | Aromatic carboxylic acids |
-
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- 2007-10-31 US US11/930,578 patent/US7488843B1/en not_active Expired - Fee Related
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| CN102115353A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院大连化学物理研究所 | Method for selective oxidization of aromatic hydrocarbons |
| CN102115353B (en) * | 2009-12-30 | 2014-11-26 | 中国科学院大连化学物理研究所 | Method for selective oxidization of aromatic hydrocarbons |
| CN105152830A (en) * | 2015-09-15 | 2015-12-16 | 河南师范大学 | Method for synthesizing ketone compound |
| CN105152830B (en) * | 2015-09-15 | 2016-09-28 | 河南师范大学 | A kind of synthetic method of ketone compounds |
| CN108467342A (en) * | 2018-04-08 | 2018-08-31 | 中南大学 | A kind of method of ultrasonic wave assisted oxidation benzyl alcohol class compound synthesis benzoic acid derivative |
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| CN108610251A (en) * | 2018-05-08 | 2018-10-02 | 宁波大学 | A kind of efficient aromatic hydrocarbons catalysed oxidation processes |
| CN111777556A (en) * | 2020-07-15 | 2020-10-16 | 遂成药业股份有限公司 | Method for preparing acridine 9-carboxylic acid by oxidation method |
| CN111777556B (en) * | 2020-07-15 | 2022-08-19 | 遂成药业股份有限公司 | Method for preparing acridine 9-carboxylic acid by oxidation method |
| CN112321414A (en) * | 2020-10-13 | 2021-02-05 | 华南理工大学 | Method for preparing benzene carboxylic acid by methyl-substituted benzene liquid-phase oxidation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101423469B (en) | 2012-05-23 |
| US7488843B1 (en) | 2009-02-10 |
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